Water-soluble condensation products



it densation products from phenolic substances and iti n of acids oralkalie or on o lin remain i 05 may belong to the so-called novolacs;however, Example 1 35 Patented Oct. 24, 1939 2,177,420

UNITED STATES PATENT OFFICE WATER- SOLUBLE CONDENSATION PRODUCTS HermannNoerr and Gustav Mauthe, Leverkusen-I. G. Werk, Germany, assignors to I.G. Farbenindustrie Aktiengesellschaft, Frankforton-the-Main, Germany 1No Drawing. Application December 5, 1936, Serial No. 114,364. In GermanyDecember 5, 1935 5 Claims. (Cl. 260-49) This invention relates towater-soluble consmall quantity of water and finally furthercondensation products fromphenolic substances and densing it with agentscapable of linking aromatic to a method of preparing the same. nuclei.For the latter process generally less than It is known that phenolaldehyde resins may the molecular quantity of the condensing agent 5 beconverted into water-soluble products by sul- (calculated on thesulfonated condensation prodfonation. However, in order to achieve thisresult not) is employed, as on after-treating with an it was necessaryto'introduce a relatively great excess of the agent the products becomeless number of sulfo groups into the molecule of the soluble again.Whereas the weakly sulfonated resin. The high content of sulfo groups ofthese condensation products are not completely soluble so products issometimes disadvantageous, for inin water and whereas especially onprolonged M stance, if theproducts are to be employed as tan- S orage Oo bo g their aqueous Suspensions ning agents, since they have but asmall tanning become still more insoluble, the after-treated action inweakly acid or neutral media. products display a considerably improvedsolu- We have now discovered a new class of conbility in water; theirsolutions, even on the adcondensing agents capable of linking aromatic pct y Stttblenuclei, which contain less than. 1 suite group per Theproduc s So obt a y be p y each aromatic nucleus present therein, andnevfor Va us p p ses of industry, for instance. as ertheless arewater-soluble.- Our new products yein ag n s f r r rvi p p s agents :19may be prepared by first sulfonating a. fusibl for the after-treatmentof textile fibers and tis- 20 resin obtainable from a phenolic substanceand a Su fo exa p e, or We s t c e condensing agent capable of linkingaromatic d n agents, and espec a ly as tannin nuclei, Without renderingit water-soluble therea s- It s a y e pointed 011i? that by, and thentreating it with afurth r tit especially for the last mentioned purposeit is of m of a condensing agent, until it is water-soluble. greatimporta that 1the products in pari- As starting material for the processaccording son with their molecular weight or the number of to ourinvention we employ th se r in aromatic nuclei contained therein containbut a densation products ofphenolic substances which Small number o u Ogroup in Consequence are still fusible, i. e. are not toohigh molecularthereof, the new Water-Soluble products p ay and according to thenomenclature mostly adoptan excellent tanning action even in a Weakly 30ed in the art belong to the group of resins comacid neutralSolutionmonly called resols. These starting materials The following@Xamples illustrate the f may pref abl have been obtained by condenstion without limiting it thereto, the parts being ing the components inan acid medium, i. e. they by Weight:

also products condensed in an alkaline medium 470 gs of phenoI aregradually heated to boilas far as itv is possible to maintain theirconing ith 500 gs, f water, 250 gs. of formaldehyde densation at a lowdegree, so that they are still (te hn, 30%) and 50 gs. of 10% aqueoushyd u y be e p y for e p o ess of t e chloric acid and are kept boilingfor 5 hours. The

present invention. The single components used resin separating therefromis treated with steam 40 for building p the s n u s rting matein orderto remove the excess of phenol. The rials are phenolic substances, i. e.aromatic commass is then dried. 51 parts of the mass thus obpoundscontaining OH-groups directly linked to tained, brittle in the cold andviscous when it is an aromatic nucleus, and more especially the warmed,and consisting essentially of dihydroxyph n l prop r, their hom lo ueanalo ues and diphenylmethane (c. f. Beilstein, Suppl. Vol. VI, 45 u stu n pr du s, d, n th ot r hand, 488) are heated with 12.5 parts ofsulfuric acid condensing agents capable of linking aromatic monohydratefor 1-2 hours at about 70 C. Afnuclei, like for instance, formaldehyde,subterwards 15 parts of water of about 40 C. are stances yieldingformaldehyde, acetaldehyde, carefully added while stirring, the waterbeing chlor-acetone, dichlorether etc. evenly taken up by the mass. Now,'7 parts of 50 More particularly the process for preparing ourformaldehyde in 30 parts of water are gradually new compounds is carriedout by treating the added and the whole is heated to 40 to 50 C.

said starting materials with less than molecular until the smell offormaldehyde has disappeared.

quantities of concentrated sulfuric acid or of A clear solution isobtained which on long standother sulfonating agents mixing the masswith a ing does not separate. The dark color of the sulfonated productshas been greatly diminished by the after-treatment. The product has anaffinity for animal and plant fibers. On treating it with furtherquantities of formaldehyde it I becomes less soluble again.

Example 2 94 parts of phenol are heated with 30 parts ofmonochloracetone for 5 hours to a temperature of about 100 C. 67 partsof the resin obtained are treated with 24.5 parts of sulfuric acidmonohydrate for about 2 hours at a temperature of about 60 C. Thesulfonation mass is diluted with parts of water and after-treated with 5parts of formaldehyde (techn. 30%) in parts of water at about 50 C.until the mixture obtained displays a good solubility in water. Beforecooling a further 50 parts of water are added. A syruplike solution isobtained which may be diluted with water in any proportion without'anyprecipitation taking place.

Example 3 108 parts of crude cresol (DAB VI) are gradually heated with50 parts of formaldehyde (techn.

30%), with 200 parts of water and 10 parts of a 10% hydrochloric acid toabout 90 0., this temperature being maintained for about 5 hours. Theresin separating therefrom is carefully dried invacuo. 100 parts of themass thus obtained are treated with 45 parts of sulfuric acidmonohydrate for 1-2 hours at a temperature of about 60 C. parts of waterare slowly added to the viscous mass, while stirring. Finally the massis after-treated with 7.5 parts of acetaldehyde in 35 parts of water ata temperature of about 60 C. until the smell of acetaldehyde has nearlydisappeared. After further diluting, the mixture is neutralized withammonia and by adding formic acid a pH-valve of about 3.5 isestablished.

The solution is capable of tanning animal hides to yield light and softleathers displaying a rela tively good fastness to light.

Example 4 188 parts of phenol are caused to react with 100 parts offormaldehyde and 60 gs. of caustic soda of B. The mixture is graduallyheated to 100 C. the temperature being maintained for 4 hours. The massis then precipitated with 75 parts of a 24% hydrochloric acid, washedand well dried. 100 parts of the resin thus obtained arevtreated atabout 70 C. with parts of a 100% sulfuric acid in the course of half anhour, the temperature being maintained for about 1 hour. Then the massis diluted with parts of water and finally after-treated'with 15 partsof techn. formaldehyde in parts of water .at a temperature of about 50C. A viscous solution is obtained which may be diluted with, water inany proportion.

We claim:

1. A process for preparing water-soluble condensation products whichcomprises sulfonating a fusible condensation product derived from aphenol and an agent capable of linking aromatic nuclei selected from theclass consisting of acetaldehyde, chloracetone, dichlorether,formaldehyde and subsances yielding formaldehyde, 'while introducing atthe most one sulfonic acid group into the condensation productcalculated per every two aromatic nuclei contained therein, and withoutrendering the condensation product completely water-soluble thereby, andthen treating the sulfonated product With a further quantity of saidagent until it is completely water-soluble.

2. A process for preparing water-soluble condensation products whichcomprises sulfonating a fusible condensation product derived from phenoland formaldehyde while introducing at the most one sulfonic acid groupinto the condensation product calculated per every two benzene nucleicontained therein, and without rendering the condensation productcompletely water-soluble thereby, and then treating the sulfonatedproduct with a further quantity of formaldehyde until it is completelywater-soluble.

3. A process for preparing water-soluble condensation products whichcomp-rises sulfonating a fusible condensation product derived from acresol and formaldehyde while introducing at the most one sulfonic acidgroup into the condensation product calculated per every two benzenenuclei contained therein, and without rendering the condensation productcompletely water-insoluble thereby, and then treating the sulfonatedproduct with a further quantity of formaldehyde until it is completelywater-soluble.

4. A process for preparing water-soluble condensation products whichcomprises heating about 51 parts of a condensation product essentiallycomprising dihydroxydiphenylmethane with about 12.5 parts of sulfuricacid monohydrate for about 1 to 2 hours to about C., diluting theresulting mixture with water and heating the product thus obtained withformaldehyde until i it is completely soluble in water.

HERMANN NOERR. GUSTAV CERTIFICATE OF CORRECTION Patent No. 2,177,L 20.October at, 19 9.

HERMANN NOERR', ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,second column, line 55-56, claim 5, for the word "water-insoluble" readwatersoluble; and that the said Letters Patent should be read with thiscorrection therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 12th day of March, A. D. "19m.

Henry Van .Arsdale, (Seal) Acting Commissioner of Patents.

